N-substituted fatty acid amide lubricants

ABSTRACT

THIS INVENTION RELATES TO N-ACYLMORPHOLINES AND NMONO AND N,N-DISUBSTITUTED FATTY ACID AMIDES AND TO SIMILAR DERIVATIVES OF EPITHIOAMIDES WHICH ARE USEFUL AS BASE AND EXTREME PRESSURE LUBRICANTS AND ADDITVES.

United States Patent 3,733,275 N-SUBSTITUTED FATTY ACID AMIDE LUBRICANTS Frank C. Hague, Robert E. Mod, and Gene Sumrell,

New Orleans, La., and Winfred E. Parker, Philadelphia, Pa., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed Dec. 21, 1971, Ser. No. 210,591 Int. Cl. Cm 1/20, 1/36, 1/38 U.S. Cl. 252-463 7 Claims ABSTRACT OF THE DISCLOSURE This invention relates to N-acylmorpholines and N- mono and N,N-disubstituted fatty acid amides and to similar derivatives of epithioamides which are useful as base and extreme pressure lubricants and additives.

This application is a continuation-in-part of Ser. No. 176,734 filed Aug. 31, 1971.

A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sub-licenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to certain compounds which are N-fatty acyl derivatives of primary and second amine and N-substituted acyl derivatives of primary and secondary amines which have exhibited utility as base lubricants, extreme pressure lubricants or lube additives. More particularly, this invention relates to N- and N,N-disubstituted long chain aliphatic amides the acyl component of which is a normal, branched, or substituted alkenoic or alkanoic acyl group containing from 16 to 22 carbon atoms the amide nitrogen of which may be derived from an alkyl amine, dialkyl amine, alkyl-alkoxyalkylamine, dialkoxyalkylamine or nitrogen heteroalicylic. Typical amines are butylamines, dibutylamines, N-methyl-alkoxyethyl amine, di-ethoxyethyl amine, and morpholine. The acyl substituent referred to may be divalent sulfur or pentavalent phosphorous.

We have discovered that many of the simple N-alkyl and N,N-dialkyl or N-alkyl-N-alkoxyalkyl amines of the C to C alkeneoic or alkanoic fatty acids are good base lubricants. We have further discovered that the introduction of divalent sulfur into the fatty acid moiety imparts excellent extreme pressure lubricant characteristics to such compounds. In particular we have found the epithio group to be most effective. We have also observed that the introduction of both hydroxy and alkyl phosphate groupings alpha to each other also imparts extreme pressure lubricant characteristics to the compound.

In addition it was noted that the above hydroxy-phosphato compound and its mercapto analog N-[9(l0)-mercapto-(9) lO-dibutylphosphato]stearamide were effective antiwear compounds and additives.

Included among the specific compounds operable as base lubricants are N-methyl-N-butyloleamide, N-ethoxyethoxyethoxy propyloleamide, N-ethoxyethoxy, propyloleamide, N-methoxyisopropyloleamide, N-methoxyethyloleamide. Compounds showing particular promise as extreme pressure lubricants or additives are N,N-dibutyl- 9,10-epithiostearamide, N,N dibutyl-9,10,l2,13-diepithiostearamide, 9,10-epithiostearoyl morpholine, N-ethoxyethoxyethoxypropyl-9,l0 epithiostearamide, N-9,10,l2, 13-diepithiostearoylmorpholine and N-[9(10) hydroxy- 9( 10) -dibutylphosphato] stearamide.

3,733,275 Patented May 15,, 1973 Compounds showing particular promise as antiwear additives are N,N dibutyl-[9(10)-hydr0xy-(9)IO-dibutylphosphato1stearamide and N,N- [9 l0)mercapto-(9) l0- dibutylphosphatostearoylmorpholine.

In addition to their utility as beneficial additives for petroleum and synthetic diester base lubricants, it has more recently been discovered that some of the epithioamide and dibutyl phosphate derivatives thereof and of epoxides are useful additives for silicone fluids. Silicones in certain applications such as brass-on-brass, brass-onnickel, and bronze-on-nickel lubrication are considered good lubricants. However, in the most common metal combination, steel on steel, they are very poor. Because of their low-toxicity and non-corrosiveness and superior physical and chemical characteristics as base oils compared to petrochemicals and synthetic esters in areas such as thermal stability, viscosity characteristics and sludging it would be decidedly advantageous to upgrade their deficient load carrying and wear characteristics as lubricants for the forementioned metal surfaces.

Most additives normally employed for the improvement of extreme pressure and antiwear characteristics in petroleum and synthetic diester base oils are insoluble in silicones and therefore inelfectual. We have discovered that the amide derivatives herein described are soluble in some silicone fluids and contribute a significant improvement at the 5% level in both the extreme pressure and antiwear performance of the silicone base oil.

EXAMPLE 1 N-methyl-N-butyloleamide.-- grams (0.33 mole) of oleoyl chloride was added dropwise and with stirring to a mixture of 29 grams (0.33 mole) of N-methyl-N-butylamine and 27 grams (0.33 mole) of pyridine. Stirring was continued until the heat of reaction subsided. The solid pyridine hydrochloride was filtered 011 and the filtrate was Washed successively with aqueous HCl and water until acid free. It was dried stripped, percolated through an activated alumina column, and the product removed from the percolate by stripping off the solvent. Analysis of the product: Percent C, 78.87 (theory 78.63); percent H, 13.02 (theory 12.82); percent N, 3.96 (theory 3.99).

EXAMPLE 2 N,N-dibutyloleamide-This material was prepared by the procedure of Example 1 from 100 grams (0.33 mole) of oleoyl chloride 42.5 grams (0.33 moles) of di-n-butylamine and 27 grams (0.33 mole) pyridine. Analysis of the product: Percent C, 78.94 (theory 89.25); percent H, 13.16 (theory 13.06); percent N, 3.44 (theory 3.56) confirm the preparation.

EXAMPLE 3 Ethoxyethoxyethoxy propyloleamide.-This material was prepared by the procedure of Example 1 from 100 grams (0.33 mole) of oleoyl chloride, 73.0 grams (0.33 mole) ethoxyethoxyethoxypropylamine and 27.0 grams (0.33 mole) pyridine. Analysis of percent C, 71.84 (theory 72.04); H, 11.80 (theory 11.80), and N, 2.96 (theory 2.90) confirm the preparation.

EXAMPLE 4 Ethoxyethoxypropyloleamide.-This material was prepared by the procedure of Example 1 from 100 grams (0.33 mole) of oleoyl chloride, 58.3 grams (0.33 mole) ethoxyethoxypropylamine and 27.0 grams 0.33 mole) of pyridine. Analyses of percent C, 71.45 (theory 73.80); percent H, 11.87 (theory 12.07); and percent N, 2.92 (theory 3.18) confirm the preparation.

3 EXAMPLE 5 Methoxyisopropyloleamide.This material was prepared by the procedure of Example 1 from 100 grams (0.33 mole) of oleoyl chloride, 29.3 grams (0.33 mole) methoxyisopropylamine and 27.0 grams (0.33 mole) pyridine. Analysis of percent C, 73.15 (theory 74.99); percent H, 12.01 (theory 11.93); and percent N, 3.67 (theory 3.97) confirm the preparation.

EXAMPLE 6 Methoxyethyloleamide.This material was prepared by the procedure of Example 1 from 100 grams (0.33 mole) of oleoyl chloride, 24.4 gram (0.33 mole) of methoxyethylamine and 27.0 grams (0.33 mole) pyridine. Analysis of percent C, 73.08 (theory 74.55); percent H, 11.98 (theory 11.83); and percent N, 3.31 (theory 4.14) confirm the preparation.

EXAMPLE 7 Oleoylmorpholine.This material was prepared by the procedure of Example 1 from 100 grams (0.33 mole) of oleoyl chloride, 28.7 grams (0.33 mole) of morpholine and 27.0 grams (0.33 mole) of pyridine.

EXAMPLE 8 N,N-dibutyloleamide.This product was prepared following the exact procedure of Example 2 except for the substitution of oleoyl chloride by lineoleoyl chloride.

EXAMPLE 9 N,N-dibutyl-9,10-epithiostearamide.120 grams (0.30 mole) of N,N-dibutyloleamide was epoxidized by the addition with stirring of 62.0 grams (0.36 mole) of metachloroperbenzoic acid in 630 ml. of chloroform. Reaction Was continued for 1 hour beyond final addition and the excess peracid destroyed by a small amount of a 10% solution of Na SO The meta-chlorobenzoic acid was removed by a NaHCO wash, followed by water washing. The CHCl solution was then dried with anhydrous Na SO and the CHCl stripped off to recover the product N,N-dibutyl-9,l0-epoxystearamide, oxirane content 3.45% (theory 3.91%). 100 grams (0.24 mole) of this product was added to a well stirred slurry of 55.7 g. (0.75 moles) of thiourea and 89.5 g. (0.72 moles) of benzoic acid in acetone. Stirring was continued for 3 hours beyond the terminal addition whereupon the benzoic acid was washed out with 38.8 g. (0.36 mole) of Na CO and the organic product extracted with hexane. The organic phase extract was dried and stripped to recover the product N,N-dibutyl- 9,10-epithiostearamide containing 6.41% sulfur (theory 6.67%

EXAMPLE 10 N-(9,10-epithiostearoyl)morpholine.-This product was prepared by the exact procedure described in Example 9 except for the substitution of oleoylmorpholine for the N,N-dibutyloleamide of Example 9. Analysis of product showed percent C, 71.22 (theory 69.34); percent H, 11.22 (theory 10.77); percent N, 3.66 (theory 3.68); percent S, 3.44 (theory 7.80).

EXAMPLE 11 N,N dibutyl 9,l0,12, 14 diepithiostearamide.This product was prepared following the procedure described in Example 9 except for the replacement of the N,N-dibutyloleamide of Example 9 by N,N-dibutyllinoleamide, and a doubling of the molar ratios of all reagents. The product analyzed as follows: percent C, 69.64 (theory 68.57); percent H, 10.93 (theory 10.76); percent N, 3.10 (theory 3.07); percent S, 11.7 (theory 14.06).

EXAMPLE 12 N ethoxyethoxyethoxypropyl 9,10 epithiostearamide.To 166 g. of N-ethoxyethoxyethoxypropyl oleamide, Example 3, was added dropwise and with stirring 73.8 g. of m-chloroperbenzoic acid in 800 ml. of CHCI The spent m-chloroperbenzoic acid was removed with 10% aqueous NaI-ICO and the epoxide recovered by drying and stripping off the CHCl 171 g. of this epoxide was added dropwise to a slurry of 56 g. thiourea in 1000 ml. of acetone and the concurrent addition of 43.4 g. of glacial acetic acid and the reaction mixture stirred for 3 hours. The glacial acetic acid was neutralized with Na CO and the episulfide, N ethoxyethoxyethoxypropyl 9,10- epithiostearamide, extracted with Skellysolve B and Washed, dried, and stripped. Its elemental analysis was C==67.1 (66.52), H=11.42 (10.88), N=2.67), 2.87 s=2.29 (6.57).

EXAMPLE 13 N Ethoxyethoxyethoxypropyl 9(10)mercaptostearamide-173 g. of N-ethoxyethoxyethoxypropyloleamide in CCL, was treated in the cold with a CC].; solution containing 60.9 g. of bromine. Any unreacted bromine was removed by a thiosulfate wash. 140 g. of the resulting dibromo compound was added dropwise to a well stirred solution of 72 g. of Na S-9H O in dimethylsulfoxide maintained at C. Stirring was continued at 80 C. for 3 hours. Water was added and the reaction product was extracted with hexane; washed, dried, and stripped. Elemental analysis of the product was C=66.3 (66.5); H=11.1 (10.9), N=2.7 (2.9), S=4.4 (6.8).

EXAMPLE 14 N,N Dibutyl 9(10) [dibutylphosphono] stearamide. g. of N,N-dibutyloleamide, Example 2, 148 g. of dibutyl phosphite, and 1.29 of benzoyl peroxide catalyst were heated at C. for 3 /2 hours. Additional units of 1.29 g. of benzoyl peroxide was added after the first and second hours of reaction time. The excess dibutyl phosphite was then removed by distillation at reduced pressure, 0.45 mm. Hg. The stillpot contents showed strong adsorption bonds at 8, 9.3, and 9.7 microns characteristics of the phosphonate group. The elemental analysis was C=obs 71.46 (69.50), H=obs 12.42 (11.92), N=obs 2.20 (2.38), P=obs 4.24 (5.28) percent respectively.

EXAMPLE 15 N-9,10-12,13-diepithiostearoylmorpholine.-This product was prepared by the same procedure described in Example 9 except for the substitution of linoleoyl morpholine for the N,N-dibutyloleamide of Example 8 and the doubling of molar proportions of the m-chloroperbenzoic acid in the epoxidation step and the thiourea and benzoic acid in the epthioation step. The elemental analysis was C=obs 68.83 (63.92), H=obs 10.26 (9.44), N=3.29 (3.38), S=obs 4.00 (15.49) percent respectively.

EXAMPLE 16 N,N-dibutyl [9(10)-hydroxy-(9) IO-dibutylphosphato] stearamide.44.7 g. of dibutylhydrogen phosphate was added to 182.2 g. of N,N-dibutyl-9,10-epoxystearamide at 90-95 C. with stirring. Reaction conditions Were continued for 3 /2 hours after termination of the addition. The reaction product was dissolved in commercial hexane and the unreacted dibutyl hydrogen phosphate neutralized and Washed out with portions of aqueous 10 NaHCO followed by several water washes. Acidulation of the hexane phase with diluted HCl followed by several water washes, drying and stripping, yielded the product. Elemental analysis was, C=obs 66.56 (65.91), H=obs 11.04 (11.30), N=obs 2.90 (2.26), P=obs 3.04 (4.20).

EXAMPLE 17 N-[9,(10)mercapto (9)10 dibutylphosphatostearoyl] morpholine.12 g. of dibutylhydrogen phosphate was added dropwise with stirring to 51.0 g. of (9,10-epithiostearoyl)morpholine, the preparation of Example 10, at 8590 C. and the heating and stirring continued for 3 hours beyond the terminal addition. The reaction product was dissolved in commercial hexane and any excess or unreacted was neutralized and washed out with aqueous 10% NaHCO The hexane extract was washed several times with water dried and stripped. The elemental analysis of the product was C=obs 66.74 (69.36), H=bs 10.69 (11.05), N=obs 2.89 (3.32) S=obs 3.27 (2.17), P=obs 1.68 (2.10) percent respectively.

EXAMPLE 18 The compounds prepared in accordance to the procedures given in Examples 1 through 7 were evaluated as base lubricants in the Shell Four-Ball Wear tests following a modified procedure of ASTM D2266-67. The resulting scar diameter on the balls after running at 600 rpm. for 1 hour at 120 C. and 50 kg. load were compared with the scars obtained using commercial lubricants such as Aeroshell Mil-L-708 (di-Z-ethylhexyl sebacate and additive), Gulfpride, single G, MS, multiviscosity, and 100 sec. paraflin oil. The results of these tests are reported in Table 1.

TABLE I.AN'IIWEAR LUBRICANT PROPERTIES OF FATTY ACID AMIDES Average wear sear, mm.

With- With out addiaddi- Compound tive tive Additive 1- N,N-bis (Z-ethoxyethyl) 0.597 0.735 N,N-di -butyl-9,10-

oleamide. epithiostearamide.

2- N,N-di-n-butyl9,10- 0.842 None.

epithiostearamide.

3- Oleoylmorpholine 0. 623 0.658 Do.

4 N,N-dimethyloleamide...- 0.797 0.987 Do.

N,N-di-n-propyloleamide- 0. 908 0. 885 D0. 6 N,N-di-n-hexyloleamide.-. 0. 893 0. 898 Do. N,N-d.i-n-butylerucamide. 0.758 0.798 D0. 8.-. N,N-di-n-butyl amide of 0.798 0.958 Do.

sel. hydrogenated cottonseed fatty acids.

9-- N,N-bis(2-methoxyethyl) 0.626 0.725 Do.

oleamide.

10- N,N-dibutyloleamide..--. 0.710

11- N-oleoylt-propyl- 0. 847

piperidine.

12- Morpholide of sel. hydro- 0. 642

genated cottonseed fatty acids.

13- N-meth -N-buty1- 0.607

oleamide.

14. N-ethoxyethoxyethoxy- 0. 503

propyoleamide.

15. N-ethoxyethoxypropyl- 0. 526

oleamide.

16.- N-methoxyisopropyl- 0.705

oleamide.

17. N-methoxyethyloleamlde- 0.420

18- 102 sec. parafiin oil 0. 902 N-methoxyethyloleamide.

19- D.O. Do.

bobutoxyoctadecanamide.

21.- 102 sec. paraflin 011 0. 818 N-N,d1b11tyl-9(10)- carbobutoxyoctadecanamide.

23-- N-[9(10) mercapto(9)10- 0.615

dibutylphosphatostearoyllmorpholine.

24... 102 sec; parafiin oil 0.552 N-[9(10)mercapt0- (9)10dibutylph0sphatostearoyll morpholine.

25- D. 0.535 Do.

26.- N,N-dibutyl-[9(10)- 0.498

hydroxy-(9)10-dib1l tylphosphato1stearam1de. I

27- 102 sec. paraffin oil 0. 498 N,N,d1butyl-[9(l0) hydroxy-(9)10-d1 butylphosphatol stearamide.

.- N,N-dlbutyl-9(10)- 0.530

[dibutylphosphono] stearamide.

30.- N-ethoxyethoxyethoxy- 0.707

pr0pyl-9,10-epitl1iostearamide.

TABLE I.-Continued Average wear scar, mm.

With- With out 5% addiadditive tive Additive Compound N-ethoxyethoxyethoxypropyl-9(10) mercaptostearamide 32.- N-(9,10,12,13- diepithiostearoybmorpholine.

Bis (2-ethylhexyl) sebacate 0. 872

sec. parafiin oil 0. 803

Aero Shell (Mil-7808) 0. 587

Gulf Pride, Single G, MS, 0. 447

multiviseosity.

100 sec. paraflin oil 0. 813 N,N-dibutyl-9,10

12,13-diepithi0- stearamide.

Bis (Z-Bthylhexyl) sebacate 0. 836 Do.

100 sec. paraffin oil 0. 723 N-9,10-epithiostearoyl morpholine. Bis (2-ethylhexyl)sebacate Do. 100 sec. paraflin oil Bis(2-etl1ylhexy1)sebacate 0. 915 0.917 N,N-dibutyl-9,10-

dichlorostearamide. 0. 848 Do.

EXAMPLE 19 The various amides were evaluated as extreme pressure lubricants or admditives in a Shell 4-ball extreme pressure tester at 1440 PPM following AST M Procedure D2595- 67T. Loads were increased in increments of 20 kg. to weld point and the test ran for one minute or to weld whichever occurred first. Commercial hypoid fluid SAE #90 was employed as the control E. P. Lubricant. The performance of the amides tested is given in Tables II, III, and 1V.

EXAMPLE 20 Selected amides were evaluated as additives to improve both the antiwear and extreme pressure performance of silicone fluids. The base silicone fluid employed was General Electric SF 1017 and the amides were employed at a 5% additive level. The results of the antiwear and extreme pressure tests are given in Table V.

TABLE II.--EXTREME PRESSURE TESTS (ASTM Weld point No addi- With Compound tive 5% #2 1- N,N-bis (Z-ethoxyethyl) oleamide 170 2. N ,N-di-n-butyl-S),10-e pithiostearamide 300 3- Olcoyhnorpholine 120 150 4- N,N-dimethylole amide..- 120 5. N,N-di-n-propyl oleamide- 120 N,N-di-n-hexylolcamide- 120 180 7- N,N-di-n-butylerucamide 120 200 8- N,N-di-n-bntyl amide of hydrogenated cotton- 120 170 seed fatty acids. 9- N,N-bis(2-methoxyethyl) oleamide 120 10- N-methyl-N-butyloleamide 100 11- N,N-Dibutyl-Q,10-epithiostearamide 300 12- N,N-dibutyl-9,10-12,l3-diepithiostearamide 440 13. N-ethoxyethoxyethoxypropyloleamide... 120 14- Nethoxyethoxypropyloleamide 120 15- N-methoxyisopropyloleamide- 100 16. N-methoxyethylolearnide 100 17- N-9,10-epithiostearoylrnorpholine 380 18. Bis(Z-ethylheXyDsebacate- 120 19.--. 100 sec. paralfin oil 100 20- SAE #90 commercial hypoid fluid. 280

TAB LE III Evaluation of N-dibutyl-Q, 10-12, 13-di-eplthiostearamide as an additive and as a base oil in extreme pressure tests. (ASTM D2596-67T) Percent Wear scar, Base oil additive Load, kg. :mm.

100 sec. parallin oil 5 140 1.00 Do 5 200 2.35 5 220 2. 75 5 2 5 120 1. 51 5 180 1. 59 5 1 190 2.47 5 200 3 10 240 2. 88 10 260 3. 55 Do 10 270 4 N,N dibutyl1-0, 10-12, 13-

diepitliiostcaramido None +120 1. 38 Do None 160 1. 61 Do None 200 1. 89 Do None 280 +2. 13 D None 320 2. 47 Do None 360 2. 70 Do None 400 2. 88 Do None 440 I Extreme pressure tests on N-ethoxyethoxyethoxypropyl-Q, 10-epi thiostearamide (PO-O-No. 7682) Applied Average Base oil Additive load sear, mm.

None 120 1. None 160 1. 75 None 240 2. 35 None 300 2. 19 None 340 2. 55 None 360 2. 62 None 380 Weld 7682 (5%) 120 2. 28 7682 (5%) 140 2. 46 7682(5%) 150 Weld 7682 (5%) 120 2. 23 7682 (5%) 140 +2. 44 7682(5%) 150 Weld Extreme pressure tests on N-ethoxyethoxyetlggggpropyl-e()-mercaptostearamide (PC-O-No.

None 200 1. 54 None 300 2. 26 None 400 2. 25 None 450 2. None 500 6 2. 15 7683 (5 120 1. 97 7683(5%) 140 2. 35 7683 (5%) 6 150 2. 54 7683(5%) 160 Weld 7683(5%) 120 1. 68 7683 (5%) 140 2. 18 7683 (5%) 160 2. 50 7683(5%) 170 2. 72 7683(5%) 180 Weld Extreme pressure tests on N-(9,10-12,13-diepithiostearoyl)morpholine (PC-O-No. 7684) None 200 2.21 None 260 2.38 None 340 2.43 None 400 2.75 None 460 2. 90 None 500 2.98 7684 (5%) 100 2.23 7684 (5%) 120 2.61 (5%) 130 2.74

7684 (5%) 140 Weld 7684 (5%) 120 2.54 7684 (5%) 140 2.58 7684 (5%) 150 Weld 7684 (5%) 140 2.53 7684 (5%) 160 2.77 7684 (5%) 170 Weld Extreme pressure tests on N,N-dibutyl-9(10)-dibutylphosphono)stearamide (PC-O-No. 7685) TABLE III.Continued Extreme pressure tests on N-[9(10)-mercapto-9(10)-dibutylphosphatostearoyl1morpholine (OC-O-No. 7687) None 120 0. 608 None 160 1. 45 None 200 1. 40 None 240 1. 70 None 280 7 3. 36

Extreme pressure tests on N ,N-dibutyl-O(10)-carbobutyoxyoctadeca11- amide (P C-O-No. 7688) None 1. 92 None 2. 18 None 2. 45 None Weld 1 Incipient seizure- 7 5 seconds.

8 4 seconds.

i 10 seconds.

5 46 seconds.

6 Test stopped because of extreme decomposition. Did not weld.

7 Test stopped because of extreme dccomptosiion and noxious fumes. Did not weld.

TABLE IV Evaluation of N-9,10-epithiostearoyl morpholine as an additive and as a base oil in extreme pressure tests (ASTM D 2596-67T) Percent Wear scar, Base oil additive Load, kg. m.

100 Sec. paraifin oil. 5 120 2.00 D 5 2. 80 5 3. 25 5 1 Weld 5 80 1. 57 5 120 2. 03 5 140 2. 41 5 160 2. 94 5 180 3.00 5 200 l Wcld None 120 0.70 None 200 2. 13 None 240 2. 43 None 300 2. 68 None 380 3 Weld l 10 sec. 1 5 sec. 3 50 sec.

TABLE V Antiwear and extreme pressure performance of some amide additives in silicone base lubricants Average El.

Additive Load, wear scar, weld pt.,

Base oil 5% kg. mm. kg.

General Electric SF 1017...- None 5 2. 36 130 Do None 50 4.16 Do 7541 5 1. 38

Do- 7642 50 3. 07 180 Do- 7684 5 1. 62 Do 7684 50 3. 36

D0 7686 5 1. 41 160 Do 7686 50 3. 54

Do 7687 5 1.34 200 Do. 7687 50 3. 52

1 Additives: 7641N-9,10-epithiostcaroylmorpholine; 7642N,N-

dibutyl-9,10,12,13-diepithiostearamide; 7684N-(9,10,12,13-diepithiostear- OYDIHOIpllOllHB, 7686N,Ndibutyl-[9(10)-hydroxy-(9)10-dibutyphosphato]stearamide; 7687-N ,N-[9(10) mercapto-(Q) IOdibutylphosphatostcaroyllmorpholine.

Nora-At 5 kg. load, sample 7642 reduced the wear scar of SF 1017 from 2.36 mm. (no additive) to 0.41. The other samples also exhibited antiwear additive propertim; however, these did not reduce the sear diameters to acceptable levels. Samples 7642 and 7687 also have good E.P. additive properties in SF 1017. Samples 7641 and 7684 were not as effective.

We claim:

1. A composition of matter useful as a base and extreme pressure lubricant, said matter consisting of a silicone base lubricant and 5-10 weight percent of an N,N-disubstituted epithioamide selected from the group consisting of N,N-dibutyl-9,10-12,13-diepithiostcaramide and N, N-dibutyl-[9(10) -hydroxy (9) 10 dibutylphosphato]- stearamide.

2. The process of claim 1 wherein the N,N-disubstituted epithioamide is N,N-dibutyl 9,10 12,13-diepithiostearamide.

3. The process of claim 1 wherein the N,N-disubstituted epithioamide is N,N-dibutyl-[9( 10) -hydroxy- (9) IO-dibutylphosphato1stearimide.

4. A composition of matter useful as a base and extreme pressure lubricant, said matter consisting of a silicone base lubricant and 5-10 weight percent of an N-epithioacyl 9 10 morpholine selected from the group consisting of N,N- References Cited [9(10)mercapto (9) 10 dibutylphosphatostearoyl]morpholine, N-9,10-epithi0stearoyl morpholine and N-(9,10- UNITED STATES PATENTS 12,13-diepithiostearoyl)morpholine. 2,722,518 11/1955 Watson 252-463 5. The process of claim 4 wherein the N-epithioacyl 5 3,278,649 10/1966 Bamas 252-467 morpholine is N,N [9(10)mercapto-(9) IO-dibutylphos- 3317426 5/1967 Lowe 252-46] phatosteamyl] m0rpho1ine 3,321,401 5/1967 Ford et a1. 252-46.7 6. The process of claim 4 wherein the N-epithioacyl morpholine is N-9,10-epithiostearoy1 morpholine. WERTEN BELLAMY Pnmary Exammer 7. The process of claim 4 wherein the N-epithioacyl 10 morpholine is N (9,10-12,13-diepithi0stearoy1)morpholine. 25246.7, 51.5 A 

